TW201500501A - Pressure-sensitive adhesive layer for optical applications, pressure-sensitive adhesive layer-attached optical film, and image display device - Google Patents

Abstract

A pressure-sensitive adhesive layer for optical applications of the present invention is made from a pressure-sensitive adhesive for optical applications including a base polymer (A), and the pressure-sensitive adhesive layer for optical applications includes iodine and/or iodide ions (B). The pressure-sensitive adhesive layer for optical applications has an antistatic function and can satisfy a durability.

Description

Optical adhesive layer, optical film with adhesive layer and image display device Technical field

The present invention relates to an optical film for an optical adhesive layer and an adhesive layer having an optical adhesive layer.

Examples of the optical film used in the optical film with an adhesive layer of the present invention include a polarizing film, a phase difference plate, an optical compensation film, a brightness enhancement film, and a laminate of these. The optical film with an adhesive layer of the present invention is suitable for optical applications, for example, for liquid crystal display devices, organic EL (electroluminescence) display devices, PDP (plasma display panels), electronic paper and other image display devices, and touch In the manufacturing use of input devices such as panels.

Background technique

In the liquid crystal display device or the like, it is indispensable to arrange a polarizing element on both sides of the liquid crystal cell in accordance with the image forming method, and a polarizing film is generally adhered. When the polarizing film is adhered to the liquid crystal cell, an adhesive is usually used. Further, in order to bond the polarizing film and the liquid crystal cell, in order to reduce the loss of light, an adhesive is used to adhere the respective materials. In such a case, based on the advantage that there is no need for a drying step when the polarizing film is adhered, it is generally used to use an adhesive. The polarizing film of the adhesive layer on the side of the polarizing film is previously provided in the form of an adhesive layer. A release film is usually attached to the adhesive layer of the polarizing film with the adhesive layer.

When the liquid crystal display device is manufactured, when the polarizing film with the adhesive layer is attached to the liquid crystal cell, the release film is peeled off from the adhesive layer of the polarizing film to which the adhesive layer is attached, but the peeling of the release film may cause Static electricity is generated. The static electricity thus generated affects the orientation of the liquid crystal inside the liquid crystal display device and causes defects. Further, when a liquid crystal display device is used, display unevenness may occur due to static electricity. The generation of static electricity can be suppressed, for example, by forming an antistatic layer on the outer surface of the polarizing film, but the effect is poor, and there is a problem that static electricity cannot be prevented from being fundamentally prevented. Therefore, in order to suppress the occurrence of static electricity, it is necessary to impart an antistatic function to the adhesive layer. As means for imparting an antistatic function to the adhesive layer, for example, a method of blending an ionic compound into an adhesive forming an adhesive layer has been proposed (Patent Documents 1 and 2). Patent Document 1 describes a scheme in which an ionic solid containing an imidazolium cation and an inorganic anion is blended in an acrylic adhesive for a polarizing film; and Patent Document 2 discloses that a quaternary nitrogen atom is contained. An organic molten salt which is a liquid at room temperature, such as a cation having a carbon number of 6 to 50 and an anion of a fluorine atom, is blended in an acrylic adhesive used for a polarizing film. Further, a method of providing an antistatic layer between a polarizing film and an adhesive layer using an adhesive of a conductive polymer such as polythiophene has been proposed (Patent Document 3). In addition, the polarizing film with an adhesive layer requires durability in a bonded state.

Prior art literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-251281

Patent Document 2: International Publication No. 2007/034533

Patent Document 3: Japanese Laid-Open Patent Publication No. 2003-246874

Summary of invention

In Patent Documents 1 and 2, an antistatic function is imparted by applying an adhesive layer formed of an adhesive composition containing an ionic compound to a polarizing film. However, in order to impart an antistatic function to an existing adhesive composition containing an ionic compound, it is necessary to add a relatively large amount of an ionic compound, which may adversely affect the durability of the adhesive. Further, as shown in Patent Document 3, when a layer containing a conductive polymer such as polythiophene is provided between the polarizing film and the adhesive layer, the number of steps increases and the conductive polymer is expensive, resulting in an increase in cost.

Further, as the polarizing film with the adhesive layer, a polarizing film in which a transparent protective film is provided only on the side of the polarizer and an adhesive layer is provided on the other side without providing a transparent protective film and an adhesive layer may be used. The polarizing film with the adhesive layer has a transparent protective film on only one side, so that the cost of a portion of the transparent protective film can be reduced as compared with the case where the transparent protective film is provided on both sides. However, in the case where the adhesive layer contains an ionic compound, the ionic compound in the adhesive layer sometimes affects the polarizing member and the adhesive property, for example, when a large amount of an ionic liquid and an ionic solid are used as the ionic compound. , fearing that the polarizer will deteriorate and light will occur. Adverse conditions such as reduced durability and peeling under high temperature humidification.

An object of the present invention is to provide an optical adhesive layer which has an antistatic function and can satisfy durability.

Further, an object of the present invention is to provide an optical film having an adhesive layer containing the above-mentioned optical adhesive layer, and to provide an image display device using the polarizing film with the above-mentioned adhesive layer.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found the following optical adhesive layer, and have completed the present invention.

That is, the present invention relates to an optical adhesive layer comprising an optical adhesive containing a base polymer (A) and containing iodine and/or iodide ions (B).

The optical adhesive layer preferably contains 0.02 to 1 atom% of the above iodine and/or iodide ion (B).

In the optical adhesive layer, the base polymer (A) is preferably a (meth)acrylic polymer. Further, the base polymer (A) preferably contains a hydroxyl group. As the (meth)acrylic polymer, those having a (meth)acrylic acid alkyl ester and a hydroxyl group-containing monomer as a monomer unit can be used.

Further, the base polymer (A) preferably contains a carboxyl group. As the (meth)acrylic polymer, those having a (meth)acrylic acid alkyl ester and a carboxyl group-containing monomer as a monomer unit can be used.

In the case where the (meth)acrylic polymer contains butyl (meth)acrylate as the (meth)acrylic acid alkyl ester used as a monomer unit, the optical adhesive layer preferably contains 0.01 to 3 (I). ^- /C ₃ H ₃ O ₂ ^- ) of the aforementioned iodine and/or iodide ion (B).

In the optical adhesive layer, the optical adhesive may further contain an ionic compound (C). The ionic compound (C) is preferably an alkali metal salt and/or an organic cation-anion salt.

In the above-mentioned optical adhesive layer, the optical adhesive may further contain an antioxidant (D).

In the optical adhesive layer, the optical adhesive may further contain a crosslinking agent (E).

In the optical adhesive layer, the optical adhesive may further contain a decane coupling agent (F).

Further, the present invention relates to an optical film having an adhesive layer, comprising: an optical film; and the optical adhesive layer provided on at least one side of the optical film.

In the optical film with the adhesive layer described above, a polarizing film can be used as the optical film. The polarizing film is preferably an iodine-based polarizing film having a transparent protective film on at least one side of the iodine-based polarizing member containing iodine and/or iodide ion (B). The iodine-based polarizer preferably contains 3 to 10% by weight of iodine and/or iodide ion (B). Further, as the polarizing film, a polarizing film having a transparent protective film only on the side of the polarizing member can be used, and a polarizing film obtained by disposing the above-mentioned adhesive layer on the side of the polarizing member which does not have one side of the transparent protective film can be used. .

Further, the present invention relates to an image display device characterized in that at least one of the above-mentioned polarizing films with an adhesive layer is used.

The optical adhesive layer of the present invention is formed using an optical adhesive containing a base polymer (A) and contains iodine and/or iodide ions (B). It is considered that iodine exists in an equilibrium state of iodine molecules (I ₂ ) and iodide ions (I ⁻ , I ³⁻ , I ^5- ) in the adhesive layer. The iodine and/or iodide ion (B) exists in the form of ionized iodine in the adhesive layer, so that the surface resistance value of the adhesive layer can be lowered, and the adhesion can be achieved by a simple means without increasing the number of steps. The agent layer imparts antistatic properties. Further, it is considered that the presence of iodide ions allows the cationic component (for example, potassium ion or other cationic component) to be stably present in the adhesive, and the ionic conductivity of the cationic component improves the antistatic property. Further, even when iodine and/or iodide ions (B) are present in the adhesive layer, the durability is not impaired.

In addition, since the iodide ion is polarized, the polarity becomes high, and by using a polymer having a polar group such as a hydroxyl group or a carboxyl group as the base polymer (A), the iodide ion can be stabilized. Further, the ionic compound (C) is added in a small amount to the extent that the durability is not affected, and the antistatic function can be improved.

Further, in the case where a polarizing film having a transparent protective film only on the side of the polarizing member is used as the optical film, and the adhesive layer is provided on the side of the polarizing member which does not have one side of the transparent protective film, the adhesive layer and the polarizing member Since it is in contact with the ionic compound (C), the optical properties such as the degree of polarization may be lowered. In the present invention, since the adhesive layer contains iodine and/or iodide ions (B), even when the ionic compound (C) is contained, it is possible to effectively impart optical characteristics such as the degree of polarization without being lowered. Antistatic.

Form for implementing the invention

The optical adhesive layer of the present invention is formed of an optical adhesive containing a base polymer (A) and contains iodine and/or iodide ions (B).

The above-mentioned optical adhesive can use various adhesives in accordance with the base polymer (A). Examples thereof include a rubber-based adhesive, an acrylic adhesive, a polyoxynoxy adhesive, a polyurethane adhesive, a vinyl alkyl ether adhesive, a polyvinyl alcohol adhesive, and a polyvinylpyrrolidone adhesive. A polypropylene amide-based adhesive, a cellulose-based adhesive, or the like. The adhesive base polymer (A) can be selected in accordance with the type of the aforementioned adhesive.

Further, since the base polymer (A) stabilizes iodide ions in the adhesive layer, it is preferred to have a polar group such as a hydroxyl group or a carboxyl group. Among these polar groups, a hydroxyl group is preferred.

Among the above-mentioned adhesives, an acrylic adhesive is preferably used because it has excellent optical transparency and exhibits adhesive properties such as appropriate wettability, cohesiveness, and adhesion, and has excellent weather resistance and heat resistance. The acrylic adhesive contains a (meth)acrylic polymer as a base polymer. The (meth)acrylic polymer usually contains an alkyl (meth)acrylate as a main component in terms of a monomer unit. In addition, (meth)acrylate means an acrylate and / or a methacrylate, and (meth) of this invention is the same thing.

As the main skeleton constituting the (meth)acrylic polymer The alkyl acrylate may, for example, be a linear or branched alkyl group and have a carbon number of from 1 to 18. For example, the aforementioned alkyl group can be exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl , mercapto, fluorenyl, isodecyl, dodecyl, isotetradecyl, lauryl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. . They can be used alone or in combination. These alkyl groups preferably have an average carbon number of from 3 to 9.

In addition, from the viewpoints of adhesion characteristics, durability, adjustment of phase difference, adjustment of refractive index, etc., an aromatic ring such as phenoxyethyl (meth)acrylate or benzyl (meth)acrylate can be used. Alkyl (meth)acrylate. The alkyl (meth)acrylate containing an aromatic ring may be used in combination with the above-exemplified (meth)acrylic polymer after being polymerized, but contains an aromatic ring from the viewpoint of transparency. The alkyl (meth)acrylate is preferably used in combination with the aforementioned alkyl (meth)acrylate.

The ratio of the aromatic ring-containing (meth)acrylic acid alkyl ester in the (meth)acrylic polymer can be in the weight ratio of the total constituent monomer (100% by weight) of the (meth)acrylic polymer. It is contained in a ratio of 50% by weight or less. Further, the content of the (meth)acrylic acid alkyl ester containing an aromatic ring is preferably from 1 to 35% by weight, more preferably from 1 to 20% by weight, still more preferably from 7 to 18% by weight, even more preferably from 10 to 16% by weight. Better yet.

In the (meth)acrylic polymer, in order to improve adhesion and heat resistance, one or more kinds of comonomers having a polymerizable functional group may be introduced by copolymerization, and the polymerizable functional group may have (meth) propylene. An unsaturated double bond such as a mercapto group or a vinyl group. As a specific example of such a comonomer, for example, Illustrative: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, (methyl) a hydroxyl group-containing monomer such as 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, or (4-hydroxymethylcyclohexyl)-methyl acrylate; a carboxyl group-containing monomer such as methyl methacrylate, carboxyethyl (meth) acrylate, carboxy amyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid; Anhydride-containing monomer such as dianhydride or itaconic anhydride; caprolactone adduct of acrylic acid; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)propenylamine-2-methylpropanesulfonic acid a sulfonic acid group-containing monomer such as (meth) acrylamide propyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) propylene phthaloxy naphthalene sulfonic acid; 2-hydroxyethyl acryl decyl phosphate Such as a phosphate-containing monomer or the like.

Further, examples of the monomer for the purpose of modification include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N-butyl(meth)acrylonitrile. A (N-substituted) guanamine monomer such as an amine or N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide or the like; an aminoethyl (meth) acrylate; (A) alkylaminoalkyl (meth) acrylate such as N,N-dimethylaminoethyl (meth)acrylate or tertiary butylaminoethyl (meth)acrylate; An alkoxyalkyl (meth) acrylate monomer such as methoxyethyl acrylate or ethoxyethyl (meth) acrylate; N-(methyl) propylene oxymethylene butadiene Imine or N-(methyl)propenyl fluorenyl-6-oxyhexamethylenebutaneimine, N-(methyl)propenyl-8-oxomethylidenebutaneimine, N -acrylonitrile Butyldiamine-based monomer such as porphyrin; N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N- a maleimide monomer such as phenyl maleimide; N-methyl itaconimine, N-ethyl itaconide, N-butyl itaconide , N-octyl ketamine, N-2-ethylhexyl ketimine, N-cyclohexyl ketimine, N-lauryl ketimine, etc. Monomers, etc.

Further, as the modifying monomer, vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine can also be used. Vinyl pipe Vinylpyr , vinyl pyrrole, vinyl imidazole, vinyl Azole, vinyl Vinyl, N-vinylcarboxylic acid decylamine, vinyl monomer such as styrene, α-methylstyrene, N-vinyl caprolactam; cyanoacrylate such as acrylonitrile or methacrylonitrile Monomer; epoxy-containing acrylic monomer such as glycidyl (meth)acrylate; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxy (meth)acrylate a glycol-based acrylate monomer such as a glycol ester or a methoxypolypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, or polyoxy(meth)acrylate An acrylate monomer such as an ester or 2-methoxyethyl acrylate. Further, isoprene, butadiene, isobutylene, vinyl ether or the like can be given.

Further, examples of the copolymerizable monomer other than the above include a halogen-containing decane-based monomer. Examples of the decane-based monomer include 3-propenyloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, and 4-vinylbutyltrimethoxydecane. 4-vinylbutyltriethoxydecane, 8-vinyloctyltrimethoxydecane, 8-vinyloctyltriethoxydecane, 10-methylpropenyloxydecyltrimethoxydecane , 10-propenyloxydecyltrimethoxydecane, 10-methylpropane Ethyloxydecyltriethoxydecane, 10-propenyloxydecyltriethoxydecane, and the like.

Further, as the comonomer, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol may also be used. A diglycidyl ether di(meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol tri (meth) acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa a polyfunctional monomer having two or more unsaturated double bonds such as a (meth) acrylonitrile group or a vinyl group, such as an esterified product of (meth)acrylic acid and a polyhydric alcohol such as a methyl acrylate; or a polyester (meth)acrylic acid obtained by adding two or more unsaturated double bonds such as a (meth)acryl fluorenyl group or a vinyl group as a functional group similar to a monomer component to a skeleton such as epoxy or urethane. Ester, epoxy (meth) acrylate, ethyl urethane (meth) acrylate, and the like.

In the (meth)acrylic polymer, the ratio of the aforementioned comonomer in the (meth)acrylic polymer is based on the weight ratio of the total constituent monomers to the alkyl (meth)acrylate as a main component. It is not particularly limited, and the ratio of the comonomer is preferably from 0 to 20% by weight of the total constituent monomer, more preferably from about 0.1 to 15%, still more preferably from about 0.1 to 10%.

Among these comonomers, a polar group-containing monomer such as a hydroxyl group-containing monomer or a carboxyl group-containing monomer is preferably used from the viewpoint of stability of iodide ion, adhesion, and durability. In particular, a hydroxyl group-containing monomer is preferred. The hydroxyl group-containing monomer and the carboxyl group-containing monomer may be used in combination. In the optical adhesive containing a crosslinking agent In this case, these comonomers become the reaction sites with the crosslinking agent. Since the hydroxyl group-containing monomer, the carboxyl group-containing monomer, and the like are rich in reactivity with the intermolecular crosslinking agent, it is preferably used to improve the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer. The hydroxyl group-containing monomer is excellent in reworkability, and the carboxyl group-containing monomer is excellent in both durability and reworkability. The proportion of the monomer having a polar group is preferably from about 0.01 to 20% by weight of the total constituent monomer, more preferably from about 0.1 to 10%, still more preferably from about 0.5 to about 7%.

As the comonomer, in the case of containing a hydroxyl group-containing monomer, the ratio thereof is preferably from 0.01 to 15% by weight, more preferably from 0.03 to 10% by weight, still more preferably from 0.05 to 7% by weight. The comonomer preferably has a ratio of 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, more preferably 0.2 to 6% by weight, in the case of containing a carboxyl group-containing monomer.

The (meth)acrylic polymer of the present invention usually uses a (meth)acrylic polymer having a weight average molecular weight of 500,000 to 3,000,000. When considering durability, particularly heat resistance, a (meth)acrylic polymer having a weight average molecular weight of 700,000 to 2.7 million is preferably used. Further, 800,000 to 2.5 million is preferred. If the weight average molecular weight is less than 500,000, it is not preferable in terms of heat resistance. Further, when the weight average molecular weight is more than 3,000,000, a large amount of a diluting solvent is required in order to adjust the viscosity for coating, so that the cost is increased, which is not preferable. In addition, the weight average molecular weight is a value calculated by GPC (gel permeation chromatography) and calculated from polystyrene conversion.

A known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be appropriately selected for the production of such a (meth)acrylic polymer. In addition, the obtained (meth)acrylic polymer may be none Any one of a copolymer, a block copolymer, a graft copolymer, and the like.

In the solution polymerization, for example, ethyl acetate, toluene or the like can be used as the polymerization solvent. As a specific example of solution polymerization, a polymerization initiator is added under an inert gas flow such as nitrogen, and the reaction is usually carried out under the reaction conditions of about 50 to 70 ° C for about 5 to 30 hours.

The polymerization initiator, the chain transfer agent, the emulsifier, and the like used for the radical polymerization are not particularly limited, and can be appropriately selected and used. The weight average molecular weight of the (meth)acrylic polymer can be controlled by the amount of the polymerization initiator, the chain transfer agent used, and the reaction conditions, and the appropriate amount of use can be adjusted according to the type thereof.

As the polymerization initiator, and examples thereof include: 2,2 '- azobisisobutyronitrile, 2,2' - azobis (2-amidinopropane) dihydrochloride, 2,2 '- azobis Bis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2 ' -azobis(2-methylpropionate) disulfate, 2,2 '- azobis (N, N' - dimethylene isobutyl amidine), 2,2 '- azobis [N- (2- carboxyethyl) amidine] -2-methylpropanoic acid hydrate An azo initiator such as Wako Pure Chemical Co., Ltd., VA-057; persulfate such as potassium persulfate or ammonium persulfate; di(2-ethylhexyl) peroxydicarbonate or diperoxydicarbonate 4-tertiary butylcyclohexyl) ester, di(di-butyl phthalate), tertiary butyl peroxy neodecanoate, tertiary hexyl peroxybutyrate, tertiary isobutyl peroxylate Butyl ester, dilaurin peroxide, di-n-octyl peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, bis(4-methylbenzhydryl peroxide) ), peroxides such as benzamidine peroxide, tertiary butyl peroxybutyrate, 1,1-di(tri-hexylperoxy)cyclohexane, tertiary butyl hydroperoxide, hydrogen peroxide, etc. system Initiator; persulfates in combination with sodium bisulfite, a combination of a peroxide and sodium ascorbate redox system or the like obtained by combining a peroxide initiator with a reducing agent, but is not limited thereto.

The polymerization initiator may be used singly or in combination of two or more kinds thereof, and the total content thereof is preferably about 0.005 to 1 part by weight, preferably about 0.02 to 0.5 part by weight, per 100 parts by weight of the monomer.

In addition, as a polymerization initiator, for example, when the (meth)acrylic polymer of the above weight average molecular weight is produced using 2,2 ' -azobisisobutyronitrile, the polymerization initiator is preferably used in an amount relative to the single. The total amount of the body component is 100 parts by weight, and is preferably about 0.06 to 0.2 parts by weight, more preferably about 0.08 to 0.175 parts by weight.

Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, ethanethiol acid, 2-ethylhexyl ethanethioate, and 2,3-didecyl. -1-propanol and the like. The chain transfer agent may be used singly or in combination of two or more kinds, and the total content thereof is about 0.1 part by weight or less based on 100 parts by weight of the total amount of the monomer components.

In addition, examples of the emulsifier used in the emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether sulfate, and polyoxyethylene oxide. Anionic emulsifier such as sodium phenyl ether sulfate; nonionic system such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer Emulsifiers, etc. These emulsifiers may be used singly or in combination of two or more.

Further, in terms of a reactive emulsifier, as a propylene introduced An emulsifier of a radically polymerizable functional group such as a group or an allyl ether group, specifically, for example, AQUALON HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (above All are manufactured by Daiichi Industrial Co., Ltd., ADEKAREASOP SE10N (made by Asahi Chemical Co., Ltd.). Since the reactive emulsifier is incorporated into the polymer chain after the polymerization, the water resistance is improved, which is preferable. The amount of the emulsifier to be used is preferably 0.3 to 5 parts by weight based on 100 parts by weight of the total of the monomer components, and is preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.

In the optical adhesive layer of the present invention, the ratio of iodine and/or iodide ion (B) (iodine amount) can be measured by ESCA analysis. The ESCA analysis is specifically carried out by the method described in the examples. The ratio of iodine and/or iodide ion (B) (iodine amount) under ESCA analysis is preferably 0.02 to 1 atom%. When the ratio exceeds 1 atom%, there is a problem that corrosive properties of the surrounding members occur. The aforementioned ratio is preferably 0.02 to 0.5 at%, and more preferably 0.05 to 0.3 at%.

In addition, as the base polymer (A), in the case of using a (meth)acrylic polymer having an alkyl (meth)acrylate including butyl (meth)acrylate as a monomer unit, The ratio (iodine amount) of iodine and/or iodide ion (B) in the optical adhesive layer of the present invention can be measured by TOF-SIMS analysis. The TOF-SIMS analysis is specifically carried out by the method described in the examples. The ratio of iodine and/or iodide ion (B) (iodine amount) in the TOF-SIMS analysis is preferably 0.01 to 3 (I ^- /C ₃ H ₃ O ₂ ^- ). When the ratio exceeds 3 (I ^- /C ₃ H ₃ O ₂ ^- ), there is a problem that corrosive properties such as the surrounding members are generated. The above ratio is preferably 0.01 to 1 (I ^- /C ₃ H ₃ O ₂ ^- ), and further preferably 0.01 to 2 (I ^- /C ₃ H ₃ O ₂ ^- ), 0.02 to 0.5 (I ^- /C ₃ H ₃ O ₂ ^- ) is more preferable, and further 0.05 to 0.3 (I ^- /C ₃ H ₃ O ₂ ^- ) is more preferable.

In the case where the adhesive layer is directly formed on the iodine-based polarizer and the iodine and/or iodide ion (B) contained in the iodine-based polarizer is contained in the adhesive layer, the ratio can be obtained by After the adhesive layer is placed on the iodine-based polarizer, it is controlled by humidification, heating, or the like. Further, when the iodine-based polarizer is produced (during dyeing), it can be controlled by excessively containing iodine or iodide ions.

The optical adhesive layer of the present invention contains iodine and/or iodide ions (B). The iodine and/or iodide ion (B) may contain iodine and/or iodide ion (B) in the optical adhesive by blending in the base polymer (A). Iodine and/or iodide ion (B) may be blended in the form of an aqueous solution. Further, iodine and/or iodide ion (B) can be used as a solution obtained by dissolving in an organic solvent such as ethyl acetate or alcohol. Further, it may be used as a solution obtained by mixing the aqueous solution and the organic solvent.

The iodide ion can be prepared by mixing an iodinated compound with an aqueous solution (aqueous iodine solution). As the iodinated compound, for example, potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, cesium iodide, calcium iodide, tin iodide, titanium iodide, or the like can be used. An iodine-based ionic liquid, an iodine-based ionic solid, or the like. As the iodinated compound, potassium iodide is preferred from the viewpoint of cost and characteristics.

The iodine concentration in the aqueous iodine solution is about 0.01 to 10% by weight, more preferably 0.02 to 5% by weight, more preferably 0.02 to 0.5% by weight. The concentration of the iodinated compound is preferably used in an amount of about 0.1 to 10% by weight, more preferably 0.2 to 8% by weight. Iodine and iodide can be mixed in any ratio.

Further, the iodine and/or iodide ion (B) contained in the optical adhesive layer of the present invention may be contained in the optical adhesive layer for a predetermined period of time. For example, when an adhesive layer is directly formed on the iodine-based polarizer (that is, in the case of forming an iodine-based polarizing film having an adhesive layer having only one transparent protective film), the iodine contained in the iodine-based polarizer and / or the iodide ion (B) is transferred to the adhesive layer, and the adhesive layer may contain iodine and/or iodide ions (B).

The optical adhesive of the present invention may contain an ionic compound (C). As the ionic compound (C), an alkali metal salt and/or an organic cation-anion salt is preferably used. As the alkali metal salt, an organic salt of an alkali metal and an inorganic salt can be used. In the present invention, the term "organic cation-anion salt" means an organic salt, that is, a salt having a cationic portion composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. The "organic cation-anion salt" may also be referred to as an ionic liquid or an ionic solid.

<alkali metal salt>

Examples of the alkali metal ion constituting the cation portion of the alkali metal salt include ions of lithium, sodium, and potassium. Among these alkali metal ions, lithium ions are preferred.

The anion portion of the alkali metal salt may be composed of an organic substance or an inorganic substance. As the anion portion constituting the organic salt, for example, CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₃ C ^- , C ₄ F ₉ SO ₃ ^{- may be used.} , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , -O ₃ S(CF ₂ ) ₃ SO ₃ ^- , PF ₆ ^- , CO ₃ ^2- , and the following formula ( 1) to (4) indicate, etc.: (1): (C _n F _2n+1 SO ₂ ) ₂ N ^- (where n is an integer from 1 to 10), and (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (where m is an integer from 1 to 10), (3): -O ₃ S(CF ₂ ) _l SO ₃ ^- (where l is an integer from 1 to 10), (4): (C _p F _2p+1 SO ₂ )N ^- (C _q F _2q+1 SO ₂ ) (wherein p and q are integers of 1 to 10). In particular, from the viewpoint of obtaining an ionic compound having good ion dissociation properties, an anion portion containing a fluorine atom is preferably used. As the anion portion constituting the inorganic salt, Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , AsF ₆ ^- , SbF can be used. ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^-, etc. The anion moiety is preferably a (perfluoroalkylsulfonyl) quinone imine represented by the above formula (1) such as (CF ₃ SO ₂ ) ₂ N ^- or (C ₂ F ₅ SO ₂ ) ₂ N ^- . Particularly, (trifluoromethanesulfonyl) ruthenium represented by (CF ₃ SO ₂ ) ₂ N ^- is preferred.

Specific examples of the organic salt of the alkali metal include sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, and Li (CF). ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, KO ₃ S(CF ₂ ) ₃ SO ₃ K, LiO ₃ S(CF ₂ ) ₃ SO ₃ K, etc., among which LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li ( C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, etc., and Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ A fluorine-containing lithium sulfinium salt such as F ₉ SO ₂ ) ₂ N is more preferable, and a lithium salt of (perfluoroalkylsulfonyl) ruthenium is particularly preferable.

Further, examples of the inorganic salt of an alkali metal include lithium perchlorate and lithium iodide.

<Organic cation-anion salt>

The organic cation-anion salt used in the present invention is composed of a cationic component and an anionic component, and the cationic component is composed of an organic material. Specific examples of the cationic component include pyridinium cations. a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or the like.

As the anion component, for example, Cl ^- , Br ^- , I ^- , Al ^- Cl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO can be used. ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , C ₃ F ₇ COO ^- , ((CF ₃ SO ₂ )(CF ₃ CO)N ^- , -O ₃ S(CF ₂ ) ₃ SO ₃ ^- , and with the following general formula (1) to ( 4) Representation, etc.: (1): (C _n F _2n+1 SO ₂ ) ₂ N ^- (where n is an integer from 1 to 10), and (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (where m is an integer from 1 to 10), (3): -O ₃ S(CF ₂ ) _l SO ₃ ^- (where l is an integer from 1 to 10), and (4): (C _p F _2p+1 SO ₂ )N ^- (C _q F _2q+1 SO ₂ ), (wherein p and q are integers of 1 to 10), and among them, from the viewpoint of obtaining an ionic compound having good ion dissociation property In particular, it is preferred to use an anion component of a fluorine atom.

As a specific example of the organic cation-anion salt, a compound composed of a combination of the above cationic component and anionic component can be appropriately selected and used.

For example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methyl can be used. Pyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylpyridinium bis(pentafluoroethyl) Alkylsulfonyl)imine, 1-hexylpyridinium tetrafluoroborate Salt, 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethyl Oxazole tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoride Acetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium Fluorane sulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl -3-methylimidazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) methide, 1-butyl- 3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3- Methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl 3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1 -hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium Hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium Fluorophosphate, 1-hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1 -methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium tetrafluoroborate Salt, diallyldimethylammonium trifluoromethyl Alkane sulfonate, diallyldimethylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, N, N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N-methyl-N-(2-methoxy B Ammonium trifluoromethanesulfonate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl) ruthenium, N, N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) quinone imine, glycidyl trimethylammonium trifluoromethanesulfonate , glycidyl trimethylammonium bis(trifluoromethanesulfonyl) quinone imine, glycidyl trimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, 1-butylpyridinium (three Fluoromethanesulfonyl)trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-3-methylimidazolium (three Fluoromethanesulfonyl)trifluoroacetamide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (trifluoromethanesulfonyl) trifluoroacetamide , diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyl Alkyl ammonium (trifluoromethanesulfonyl) trifluoroacetamide, N,N-dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N, N - dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-pentyl ammonium bis(trifluoro Methanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-B --N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-decyl ammonium bis(trifluoromethanesulfonyl) quinone , N,N-Dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-butyl Alkyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N- Dimethyl-N-propyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-heptyl ammonium bis(trifluoromethanesulfonate Indenylamine, N,N-dimethyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-butyl- N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-pentyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N-dimethyl-N,N-dihexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-di Ethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-amyl ammonium bis(trifluoromethanesulfonate Indenylamine, N,N-diethyl-N-methyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-propyl -N-amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl propyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl amyl ammonium bis (trifluoromethyl) Sulfhydryl) quinone imine, triethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-ethylammonium bis(trifluoromethane Sulfhydryl) quinone imine, N,N-dipropyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-butyl --N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N,N-dihexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N -Dibutyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dibutyl-N-methyl-N-hexylammonium bis(trifluoromethane Sulfhydryl) quinone imine, trioctylmethylammonium bis(trifluoromethanesulfonyl)pyrene Amine, N-methyl-N-ethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylpyridine-1-indole Fluoromethanesulfonate and the like. For example, "CIL-314" (manufactured by Japan Carlit Co., Ltd.), "ILA2-1" (manufactured by Kyoei Chemical Co., Ltd.), and the like can be used.

Further, for example, tetramethylammonium bis(trifluoromethanesulfonyl) ruthenium imine, trimethylethylammonium bis(trifluoromethanesulfonyl) ruthenium imine, trimethylbutylammonium double (Trifluoromethanesulfonyl) quinone imine, trimethyl amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) ruthenium, Trimethyloctyl ammonium bis(trifluoromethanesulfonyl) quinone imine, tetraethylammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl butyl ammonium bis(trifluoromethanesulfonyl)醯imine, tetrabutylammonium bis(trifluoromethanesulfonyl) quinone imine, tetrahexylammonium bis(trifluoromethanesulfonyl) ruthenium amide, and the like.

Further, for example, 1-dimethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) fluorene Imine, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)anthracene Imine, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-methyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-ethyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) Yttrium, 1,1-dipropylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1,1-dibutylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-pentylperidine Pyridinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpiperidinium Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidine quinone (Trifluoromethanesulfonyl) quinone imine, 1-methyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis- (Trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis- (Trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(trifluoromethane Indole, hydrazide, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(trifluoromethanesulfonyl)醯imino, 1-propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpiperidinium bis(trifluoromethanesulfonyl) fluorene Imine, 1,1-dimethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl)anthracene Imine, 1-methyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl)醯imino, 1-methyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonate) Base Amine, 1-methyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) Yttrium imine, 1-ethyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonate) Iridium imine, 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoroethane sulfonate Indole, quinone imine, 1,1-dipropylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethane sulfonate Indole, quinone imine, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propylpiperidinium bis(pentafluoroethanesulfonyl)pyrene Amine, 1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl 1-ethylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1 -methyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis ( Fluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1heptylpiperidinium bis (five Fluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium double (pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium Bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butylperidine Pyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(pentafluoroethanesulfonyl) ruthenium, 1,1-dibutylpiperidinium Bis(pentafluoroethanesulfonyl) ruthenium and the like.

Further, the cationic component of the above compound may be changed to use a trimethylphosphonium cation, a triethylsulfonium cation, a tributylphosphonium cation, a trihexylphosphonium cation, a diethylmethylsulfonium cation, a dibutylethyl group. a compound of a phosphonium cation, a dimethyl sulfonium cation, a tetramethyl phosphonium cation, a tetraethyl phosphonium cation, a tetrabutyl phosphonium cation, a tetrahexyl phosphonium cation, or the like.

Further, the above bis(trifluoromethanesulfonyl) sulfinium imine may be exemplified by the use of bis(pentafluorosulfonyl) quinone imine, bis(heptafluoropropanesulfonyl) quinone imine, and bis(nonafluorobutene). Alkylsulfonyl)imide, trifluoromethanesulfonylnonafluorobutanesulfonylimine, heptafluoropropanesulfonyltrifluoromethanesulfonylimine, pentafluoroethanesulfonylhexafluorobutyrate A compound such as an alkanesulfonyl imine or a cyclohexafluoropropane-1,3-bis(sulfonyl) quinone anion or the like.

In addition, examples of the ionic compound (C) include ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, iron chloride, ammonium sulfate, and the like in addition to the above-described alkali metal salt and organic cation-anion salt. Inorganic salt. These ionic compounds (C) may be used singly or in combination of two or more.

The ratio of the ionic compound (C) in the optical adhesive of the present invention is preferably 5 parts by weight or less based on 100 parts by weight of the base polymer (A), and more preferably 0.0001 to 5 parts by weight. When the ionic compound (C) is less than 0.0001 part by weight, the effect of improving the antistatic property may be insufficient. The ionic compound (C) is preferably 0.01 parts by weight or more, and more preferably 0.1 parts by weight or more. On the other hand, when the ionic compound (C) is more than 5 parts by weight, the durability may be insufficient. The ionic compound (C) is preferably 3 parts by weight or less, and more preferably 1 part by weight or less. The ratio of the ionic compound (C) can be set to a preferred range by using the above upper limit or lower limit.

The optical adhesive of the present invention may contain an antioxidant (D). The antioxidant (D) is excellent in improving the durability of the adhesive layer. Examples of the antioxidant (D) include phenol-based, phosphorus-based, sulfur-based, and amine-based antioxidants. Among these, phenolic antioxidants are preferred.

Specific examples of the phenolic antioxidant include, as the monocyclic phenol compound, 2,6-ditributylbutylphenol, 2,6-ditributyl-4-ethylphenol, and 2, 6-Dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-tripentyl-4-methylphenol, 2,6-2-3 Octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-tertiary butylphenol, 2-tributyl -4-ethyl-6-trioctyl phenol, 2-isobutyl-4-ethyl-6-trihexyl phenol, 2-cyclohexyl-4-n-butyl-6-isopropyl phenol, Styrene mixed cresol, DL-α-tocopherol, stearyl β-(3,5-ditributyl-4-hydroxyphenyl)propionate, etc.; as a bicyclic phenol compound, it can be mentioned 2,2 ' -methylenebis(4-methyl-6-tertiary butylphenol), 4,4 ' -butylene bis(3-methyl-6-tertiary butylphenol), 4,4 ' -Thiobis(3-methyl-6-tertiary butylphenol), 2,2 ' -thiobis(4-methyl-6-tertiary butylphenol), 4,4 ' -Methylene bis (2,6-di-tert.butyl phenol), 2,2 '- methylenebis [6- (1-methylcyclohexyl) p-cresol], 2,2' - Ethyl (4,6-di-tert.butyl phenol), 2,2 '- butylidene bis (2-tert.butyl-4-methylphenol), 3,6-dioxo-octamethylene Bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[3-(3-tri-tert-butyl-5-methyl-4) -hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-ditributyl-4-hydroxyphenyl)propionate], 2,2 ' -thio Diethyl bis[3-(3,5-ditributyl-4-hydroxyphenyl)propionate]; as a 3-cyclic phenol compound, 1,1,3-glycol (2- Methyl-4-hydroxy-5-tributylphenyl)butane, 1,3,5-gin (2,6-dimethyl-3-hydroxy-4-tributylbenzyl) trimer Isocyanate, 1,3,5-gin[(3,5-di-tributyl-4-hydroxyphenyl)propenyloxyethyl]trimeric isocyanate, ginseng (4-tert-butyl-2,6 -Dimethyl-3-hydroxybenzyl)trimeric isocyanate, 1,3,5-trimethyl-2,4,6-parade (3,5-ditributyl-4-hydroxybenzyl)benzene Examples of the 4-ring phenol compound include hydrazine [methylene-3-(3,5-ditributyl-4-hydroxyphenyl)propionate]methane; etc.; as a phosphorus-containing phenol compound, Can be cited as double (3,5-two Level-butyl-4-hydroxybenzyl ethyl phosphonate) calcium, bis (3,5-di-tert.butyl-4-hydroxybenzyl ethyl phosphonate) nickel and the like.

Specific examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, decyltridecyl phosphite, isodecyl phosphite, and phenyl diiso. Octyl phosphite, phenyl diisodecyl phosphite, phenyl ditridecyl phosphite, diphenyl isooctyl phosphite, diphenylisodecyl phosphite, two Phenyltridecyl phosphite, triphenylphosphite, decyl (decylphenyl) phosphite, ginseng (2,4-di-tert-butylphenyl) phosphite, ginseng Ethyl ethyl phosphite, tetrakis(tridecyl)-4,4 ' -butylene bis(3-methyl-6-tertiary butyl phenol)-diphosphite, 4,4 ' - Isopropyl-diphenol alkyl phosphite (wherein the alkyl group is about 12-15 carbon atoms), 4,4 ' -isopropylidene bis(2-tert-butylphenol) ‧ bis(nonylbenzene) Phosphite, bis(biphenyl) phosphite, tetrakis(tridecyl)-1,1,3-glycol(2-methyl-5-tributyl-4-hydroxyphenyl) Alkyl diphosphite, ginseng (3,5-ditributyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4 ' -isopropylidene diphenol polyphosphite, bis (octyl) Phenyl) ‧ bis [4,4 ' -butylene bis(3-methyl-6-tertiary butyl phenol)] ‧1,6-hexanediol diphosphite, hexatridecyl- 1, 1,3-parade (2-methyl-4-hydroxy-5-tertiary butylphenol) diphosphite, ginseng [4,4 ' -isopropylidene bis(2-tert-butylphenol) 】 phosphite, ginseng (1,3-distearyloxy isopropyl) phosphite, 9,10-dihydro-9-phosphaphenanthrene-10-oxide, bismuth (2,4-di Tert-butyl phenyl)-4,4 ' -extended biphenyl bisphosphonate, distearyl pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, phenyl ‧, 4 ' -isopropylidenediphenol ‧ pentaerythritol diphosphite, bis(2,4-ditributylphenyl)pentaerythritol diphosphite, bis(2,6-ditributyl -4- Methylphenyl) pentaerythritol diphosphite and phenyl bisphenol A-pentaerythritol diphosphite.

As the sulfur-based antioxidant, a polyhydric alcohol ester of a dialkylthiodipropionate and an alkylthiopropionic acid is preferably used. The dialkylthiodipropionate used herein is preferably a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms, and further preferably a polyhydric alcohol ester of alkylthiopropionic acid. It is a polyol ester of an alkylthiopropionic acid having an alkyl group having 4 to 20 carbon atoms. In this case, examples of the polyol constituting the polyol ester include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and hydroxyethyltrimeric isocyanate. Examples of the dialkylthiodipropionate include dilaurylthiodipropionate, dimyristylthiodipropionate, and distearylthiodipropionate. Wait. On the other hand, examples of the polyhydric alcohol ester of alkylthiopropionic acid include glycerol tributyl thiopropionate, glycerol trioctyl thiopropionate, and glycerin trilauryl. Thiopropionate, glycerol tristearyl thiopropionate, trimethylolethane tributyl thiopropionate, trimethylolethane trioctyl thiopropionate, three Hydroxymethylethane trilauryl thiopropionate, trimethylolethane tristearyl thiopropionate, pentaerythritol tetrabutyl thiopropionate, pentaerythritol tetraoctyl thiopropionate, Pentaerythritol tetralauryl thiopropionate, pentaerythritol tetrastearyl thiopropionate, and the like.

Specific examples of the amine-based antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, dimethyl succinate and 1-(2-hydroxyl Polycondensate of ethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidineethanol, N,N ' ,N " ,N ''' -肆-(4,6-bis-(butyl) -(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-three -2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine ‧1,3,5-three ‧N,N ' -bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl) Polycondensate of phenyl-4-piperidinyl)butylamine, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-) 4-piperidinyl)imido}], hydrazine (2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate, 2, 2,6,6-Tetramethyl-4-piperidinylbenzoate, bis(1,2,6,6-pentamethyl-4-piperidinyl)-2-(3,5-ditri Grade butyl-4-hydroxybenzyl)-2-n-butylmalonate, bis-(N-methyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate Ester, 1,1 ' -(1,2-ethanediyl)bis(3,3,5,5-tetramethylperidazole Ketone), (mix 2,2,6,6-tetramethyl-4-piperidinyl/tridecyl)-1,2,3,4-butane tetracarboxylate, (mix 1,2, 2,6,6-pentamethyl-4-piperidinyl/tridecyl)-1,2,3,4-butane tetracarboxylate, mixed [2,2,6,6-tetramethyl 4-piperidinyl/β,β,β ' ,β ' -tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl] -1,2,3,4-butane tetracarboxylate, mixed [1,2,2,6,6-pentamethyl-4-piperidinyl/β,β,β ' ,β ' -tetrazole 3-,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl]-1,2,3,4-butanetetracarboxylate, N,N ' -Bis(3-Aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amine -6-chloro-1,3,5-three Condensate, poly[6-N- Lolinyl-1,3,5-three -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imine, N,N ' -bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 1,2-dibromoethane Alkane condensate, [N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-methyl-2-(2,2,6,6-tetramethyl-4- Piperidinyl)imido]propanamide and the like.

The ratio of the antioxidant (D) in the optical adhesive of the present invention is preferably 5 parts by weight or less based on 100 parts by weight of the base polymer (A), more preferably 0.01 to 2 parts by weight. The antioxidant (D) is preferably 0.05 parts by weight or more, more preferably 0.1 part by weight or more. On the other hand, when the antioxidant (D) is more than 5 parts by weight, the durability is lowered and the degree of crosslinking is lowered. The antioxidant (D) is preferably 1.5 parts by weight or less, more preferably 1 part by weight or less. The aforementioned anti-anti The ratio of the oxidizing agent (D) can be set to a preferred range by using the above upper limit value or lower limit value.

Further, the optical adhesive of the present invention may contain a crosslinking agent (E). As the crosslinking agent (E), an organic crosslinking agent or a polyfunctional metal chelate compound can be used. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imide crosslinking agent. The polyfunctional metal chelate is a substance obtained by covalent bonding or coordination bonding of a polyvalent metal and an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. Wait. Examples of the atom in the organic compound to carry out the covalent bonding or the coordinate bonding include an oxygen atom. Examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.

The crosslinking agent (E) is preferably an isocyanate crosslinking agent and/or a peroxide crosslinking agent. Examples of the compound of the isocyanate crosslinking agent include toluene diisocyanate, chlorophenyl diisocyanate, tetramethylene diisocyanate, decyl diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane. An isocyanate monomer such as a diisocyanate, an isocyanate compound obtained by adding these isocyanate monomers to trimethylolpropane or the like, a trimeric isocyanate compound, a biuret type compound, and a polyether polyol, a polyester polyol, An urethane prepolymer type isocyanate obtained by an addition reaction such as an acrylic polyol, a polybutadiene polyol, or a polyisoprene polyol. Particularly preferred is a polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated deuterated diisocyanate and isophorone The cyanate ester constitutes one compound in the group or a polyisocyanate compound derived therefrom. Here, one compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated deuterated diisocyanate, and isophorone diisocyanate or a polyisocyanate compound derived therefrom includes: hexamethylene di Isocyanate, hydrogenated deuterated diisocyanate, isophorone diisocyanate, polyol modified hexamethylene diisocyanate, polyol modified hydrogenated didecyl diisocyanate, terpolymer hydrogenated deuterated diisocyanate, and The polyol is modified with isophorone diisocyanate or the like. In the case of the polyisocyanate compound exemplified, the reaction with a hydroxyl group is particularly rapidly carried out by using an acid or a base contained in the polymer as a catalyst, and therefore, it is preferable to use it because it contributes to the speed of crosslinking.

As the peroxide, if it is a cross-linker of a base polymer which generates a radical active species by heating or light irradiation and advances the adhesive composition, it can be appropriately selected and used, and it is preferable to use it in consideration of workability and stability. A peroxide having a half-life temperature of from 80 ° C to 160 ° C is preferably used as a peroxide having a one-minute half-life temperature of from 90 ° C to 140 ° C.

Examples of the peroxide which can be used include di(2-ethylhexyl)peroxydicarbonate (1 minute half-life temperature: 90.6 ° C), and di(4-tributylcyclohexyl)peroxydicarbonate. Ester (1 minute half-life temperature: 92.1 ° C), di-secondary butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C), peroxy neodecanoic acid tert-butyl ester (1 minute half-life temperature: 103.5 ° C) , peroxypivalic acid tertiary hexyl ester (1 minute half-life temperature: 109.1 ° C), peroxypivalic acid tertiary butyl ester (1 minute half-life temperature: 110.3 ° C), dilaurin peroxide (1 minute half-life temperature: 116.4 ° C), di-n-octogen peroxide (1 minute half-life temperature: 117.4 ° C), 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (1 minute half-life temperature: 124.3 ° C), bis(4-methylbenzhydrazide) (1 Minute half-life temperature: 128.2 ° C), benzoic acid peroxide (1 minute half-life temperature: 130.0 ° C), tertiary butyl peroxyisobutyrate (1 minute half-life temperature: 136.1 ° C), 1, 1-two (three Grade hexylperoxy)cyclohexane (1 minute half-life temperature: 149.2 ° C) and the like. Among them, in particular, from the viewpoint of excellent crosslinking reaction efficiency, it is preferred to use bis(4-tert-butylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1 ° C) and dilaurin peroxide (1 minute half-life). Temperature: 116.4 ° C), benzoquinone peroxide (1 minute half-life temperature: 130.0 ° C), and the like.

The half life of the peroxide is an index indicating the decomposition rate of the peroxide, and means the time until the residual amount of the peroxide reaches half. The decomposition temperature at which the half-life is obtained at any time and the half-life time at an arbitrary temperature are described in the manufacturer's catalogue, for example, the "Organic Peroxide Catalogue" of the Japan Oils and Fats Co., Ltd., 9th edition (May 2003) )" and so on.

The amount of the crosslinking agent (E) to be used is preferably 0.01 to 20 parts by weight, more preferably 0.03 to 10 parts by weight, per 100 parts by weight of the (meth)acrylic polymer. In addition, when the crosslinking agent (E) is less than 0.01 part by weight, the cohesive force of the adhesive tends to be insufficient, and foaming may occur during heating. On the other hand, if it is more than 20 parts by weight, the moisture resistance is insufficient. It is easy to peel off in a reliability test or the like.

The isocyanate-based crosslinking agent may be used singly or in combination of two or more kinds thereof, and it is preferred to contain the polyisocyanate compound in an amount of 100 parts by weight based on the total amount of the (meth)acryl-based polymer. The crosslinking agent is preferably 0.01 to 2 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight. It can be appropriately contained after the suppression of the peeling force under the cohesive force and the durability test.

The peroxide may be used singly or in combination of two or more kinds, and the total amount of the peroxide is 0.01 to 2 parts by weight based on 100 parts by weight of the (meth)acrylic polymer. It is preferably contained in an amount of 0.04 to 1.5 parts by weight, more preferably 0.05 to 1 part by weight. In order to adjust workability, reworkability, crosslinking stability, peelability, and the like, it can be appropriately selected within this range.

In addition, the measuring method of the amount of decomposition of the peroxide remaining after the reaction treatment can be measured, for example, by HPLC (High Performance Liquid Chromatography).

More specifically, for example, about 0.2 g of the adhesive composition after the reaction treatment may be taken out, immersed in 10 ml of ethyl acetate, shaken at 25 ° C, 120 rpm for 3 hours, and then extracted, and then in a chamber. Allow to stand for 3 days. Then, 10 ml of acetonitrile was added, and the mixture was shaken at 25 ° C and 120 rpm for 30 minutes, and filtered through a membrane filter (0.45 μm), and about 10 μl of the thus obtained extract was injected into HPLC for analysis to obtain the amount of peroxide after the reaction treatment.

The optical adhesive of the present invention may further contain a decane coupling agent (F). Durability can be improved by using a decane coupling agent (F). Specific examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-epoxypropoxy group. An epoxy group-containing decane coupling agent such as propylmethyldiethoxydecane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-aminopropyltrimethoxydecane, N -2-(Aminoethyl)-3-aminopropylmethyldimethoxy Amine-containing decane such as decane, 3-triethoxycarbamido-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-γ-aminopropyltrimethoxydecane a coupling agent; a (meth)acrylonitrile-containing decane coupling agent such as 3-propenyloxypropyltrimethoxydecane or 3-methylpropenyloxypropyltriethoxydecane; 3-isocyanate-based C An isocyanate group-containing decane coupling agent such as a triethoxysilane or the like.

The decane coupling agent (F) may be used alone or in combination of two or more. The total content of the decane coupling agent is preferably 0.001 to 5 based on 100 parts by weight of the (meth)acrylic polymer. The parts by weight are preferably 0.01 to 1 part by weight, more preferably 0.02 to 1 part by weight, more preferably 0.05 to 0.6 part by weight. This is an amount that improves the durability and appropriately maintains the adhesion to an optical member such as a liquid crystal cell.

The optical adhesive of the present invention may further contain other known additives. For example, a powder, a dye, a surfactant, a plasticizer, or a viscosity-increasing agent such as a coloring agent or a pigment may be appropriately added depending on the intended use. Additives, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, granules, foils, etc. . In addition, a redox system to which a reducing agent is added may be employed within a controllable range.

The optical adhesive layer of the present invention is formed of the above-mentioned optical adhesive. When forming the adhesive layer, it is preferable to adjust the total amount of the crosslinking agent to be added, and to fully consider the influence of the crosslinking treatment temperature and the crosslinking treatment time.

The crosslinking treatment temperature and the crosslinking treatment time can be adjusted depending on the crosslinking agent to be used. The crosslinking treatment temperature is preferably 170 ° C or less.

Further, the crosslinking treatment may be carried out at a temperature at the drying step of the adhesive layer, or may be carried out by additionally providing a crosslinking treatment step after the drying step.

In addition, the crosslinking treatment time can be set in consideration of productivity and workability, and is usually about 0.2 to 20 minutes, and preferably about 0.5 to 10 minutes.

The optical film with an adhesive layer of the present invention is one in which an optical adhesive layer is formed on at least one surface of the optical film by using the optical adhesive.

The method of forming the pressure-sensitive adhesive layer can be produced, for example, by applying the optical adhesive to a separator which has been subjected to release treatment, drying the polymerization solvent or the like to form an adhesive layer, and then transferring the adhesive layer. A method of forming an optical film; or coating the optical film with the optical adhesive, drying a polymerization solvent or the like, and forming an adhesive layer on the optical film. In addition, when the optical adhesive is applied, one or more solvents other than the polymerization solvent may be newly added.

As the spacer which is subjected to the release treatment, a polyoxynitride release liner is preferably used. In the step of applying the optical adhesive of the present invention to the liner to form an adhesive layer, as a method of drying the adhesive, a suitable method can be suitably employed depending on the purpose. A method of heating and drying the above coating film is preferably used. The heating and drying temperature is preferably 40 ° C ~ 200 ° C, 50 ° C ~ 180 ° C is better, 70 ° C ~ 170 ° C is particularly good. By setting the heating temperature to the above range, an adhesive layer having excellent adhesive properties can be obtained.

The drying time can be suitably employed for a suitable period of time. Above drying The interval should be 5 seconds to 20 minutes, 5 seconds to 10 minutes, and 10 seconds to 5 minutes.

Further, an anchor layer may be formed on the surface of the optical film, or various easy-bonding treatments such as corona treatment and plasma treatment may be performed, and then an adhesive layer may be formed. In addition, the surface of the adhesive layer can be easily bonded.

Various methods can be used for the formation of the adhesive layer. Specific examples thereof include roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip coating, bar coating, and knife coating. A method such as a method, an air knife coating method, a curtain coating method, a lip coating method, or an extrusion coating method using a die coater or the like.

The thickness of the adhesive layer is not particularly limited and is, for example, about 1 to 100 μm. It is preferably 2 to 50 μm, more preferably 2 to 40 μm, and more preferably 5 to 35 μm.

In the case where the above-mentioned adhesive layer is exposed, the adhesive layer can be protected by using a release-treated sheet (spacer) before being used for actual use.

Examples of the constituent material of the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester film; porous materials such as paper, cloth, and nonwoven fabric; nets, foamed sheets, and metal. A suitable sheet such as a foil or a laminate thereof; and a plastic film is preferably used from the viewpoint of excellent surface smoothness.

The plastic film is not particularly limited as long as it is a film that can protect the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, and a polymethylpentene film. , polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, A polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, or the like.

The thickness of the spacer is usually 5 to 200 μm, and preferably about 5 to 100 μm. The separator may be subjected to demolding and antifouling treatment using a polyfluorene-based, fluorine-based, long-chain alkyl-based or fatty acid-amide-based release agent, cerium oxide powder, or the like, or may be coated. Antistatic treatment such as mixing type or vapor deposition type. In particular, by appropriately performing a release treatment such as polyfluorination treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator, the peeling property from the adhesive layer can be further improved.

It should be noted that the release-treated sheet for producing the optical film with the above-mentioned adhesive layer can be directly used as a spacer for the optical film with the adhesive layer, and the simplification of the steps can be achieved.

As the optical film, an optical film used for forming an image display device such as a liquid crystal display device can be used, and the type thereof is not particularly limited. For example, as an optical film, a polarizing film is mentioned. The polarizing film is generally used as a transparent protective film on one or both sides of the polarizing member. The optical adhesive of the present invention is effective when a transparent protective film is used only on the side of the polarizing member as a polarizing film. In this case, the adhesive layer may be directly disposed on the polarizing member without the transparent protective film. One side.

Further, as the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably from 1 to 7 μm. Such a thin polarizer has a small thickness unevenness, is excellent in visibility, and has a small dimensional change, so that it is excellent in durability and can be used as a thickness of a polarizing film. The current thinning aspect is also ideal.

The polarizer is not particularly limited, and various polarizers can be used. Examples of the polarizing material include a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene-vinyl acetate copolymer-based partially saponified film, which adsorbs iodine or a dichroic dye. A dichroic material, a polarizer obtained by uniaxially stretching, a polyene-based oriented film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among them, a polarizing member formed of a polyvinyl alcohol-based film and a dichroic material such as iodine is preferred.

The iodine-based polarizing material obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching can be dyed by, for example, immersing a polyvinyl alcohol-based film in an aqueous solution of iodine, and stretching it to an original length of 3 ~7 times made. It may be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like as needed. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water to be washed with water. The polyvinyl alcohol-based film is washed with water to wash the surface of the polyvinyl alcohol-based film and the anti-caking agent. In addition, the polyvinyl alcohol-based film is swelled to prevent unevenness in dyeing unevenness. The stretching may be carried out after dyeing with iodine, or may be carried out while dyeing, or may be dyed with iodine after stretching. Stretching may also be carried out in an aqueous solution or a water bath of boric acid, potassium iodide or the like.

In the case of the thin polarizer, the specification of the Japanese Patent Publication No. Sho 51-069644, JP-A-2000-338329, WO2010/100917, PCT/JP2010/001460, or Japan Special Purpose 2010 -269002 manual, Japan special wish 2010- A thin polarizing film described in the specification of No. 263692. The thin polarizing film can be obtained by a method of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) layer and a stretching resin substrate in a state of being laminated. And the steps of dyeing. According to this production method, even if the PVA-based resin layer is thin, it can be stretched under the support of the resin substrate for stretching without causing problems such as cracking due to stretching.

The thin polarizing film is preferably a thin polarizing film obtained by the following method from the viewpoint of being able to be stretched at a high magnification and capable of improving the polarizing performance, that is, a step of performing stretching in a laminated body state and performing dyeing. In the method of the step, the method of stretching in an aqueous solution of boric acid described in WO2010/100917, the specification of PCT/JP2010/001460, or the specification of Japanese Patent Application No. 2010-269002, and the specification of Japanese Patent Application No. 2010-263692, is also included. In the method of the step, it is particularly preferable to carry out the step of performing the aerial stretching step before stretching in a boric acid aqueous solution as described in the specification of Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692.

As the iodine-based polarizer, it is preferred to adjust the iodine content (the content of iodine and/or iodide ions) to a high concentration of 3 to 10% by weight. A high concentration iodine-based polarizer can be suitably applied as a thin polarizer. High-concentration iodine-based polarizers are ideal in that it is easy to transfer iodine and/or iodide ions to the adhesive layer after adhesion to the adhesive layer.

As the material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, or the like can be used. Specific examples of the thermoplastic resin include cellulose resins such as triacetonitrile cellulose, polyester resins, polyether oxime resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyimide resins. , polyolefin resin, (meth)acrylic resin, cyclic polyolefin resin A olefinic resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and the like. One or more suitable additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a colorant, and the like. The content of the above thermoplastic resin in the transparent protective film is preferably from 50 to 100% by weight, more preferably from 50 to 99% by weight, still more preferably from 60 to 98% by weight, still more preferably from 70 to 97% by weight. When the content of the thermoplastic resin is 50% by weight or less in the transparent protective film, the high transparency and the like inherent in the thermoplastic resin may not be sufficiently exhibited.

An adhesive can be used for the bonding treatment of the polarizing member and the transparent protective film. Examples of the adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, and an aqueous polyester. The above-mentioned adhesive is usually used in the form of an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of a solid component. In addition to the above, examples of the adhesive of the polarizer and the transparent protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The adhesive for the electron beam curing type polarizing film exhibits appropriate adhesion to the above various transparent protective films. Further, the adhesive used in the present invention may contain a metal compound filler.

In addition, examples of the optical film include a reflector, a semi-transmissive plate, a phase difference plate (including a wavelength plate such as 1/2 and 1/4), a viewing angle compensation film, a brightness enhancement film, and the like as a liquid crystal display device. Wait for the optical layer. it They may be used alone as an optical film, and in addition, one or two or more layers may be laminated on the polarizing film in actual use.

The optical film in which the optical layer is laminated on the polarizing film may be formed by laminating in a layer in the manufacturing process of a liquid crystal display device or the like. However, in the case where an optical film is laminated in advance, quality stability or assembly operation is performed. It is excellent in that it can improve the manufacturing steps of a liquid crystal display device and the like. The laminate may be formed by an appropriate bonding means such as an adhesive layer. When the polarizing film is bonded to another optical layer, the optical axis of the polarizing film can be set to an appropriate arrangement angle according to the target phase difference characteristic or the like.

The polarizing film with an adhesive layer of the present invention is preferably used for formation of various image display devices such as a liquid crystal display device. The formation of the liquid crystal display device can be carried out according to a conventional method. In other words, the liquid crystal display device can be formed by appropriately assembling a display panel such as a liquid crystal cell, a polarizing film with an adhesive layer, and a lighting system such as an optional illumination system, and assembling a driving circuit or the like. The polarizing film with an adhesive layer of the present invention is not particularly limited, and can be carried out according to a conventional method. As the liquid crystal cell, for example, a liquid crystal cell of any type such as a TN type, an STN type, a π type, a VA type, or an IPS type can be used.

A liquid crystal display device in which a polarizing film with an adhesive layer is disposed on one or both sides of a display panel such as a liquid crystal cell, or a liquid crystal display device such as a device using a backlight or a reflecting plate in an illumination system can be formed. In this case, the polarizing film of the adhesive layer of the present invention may be disposed on one side or both sides of the display panel of the liquid crystal cell or the like. When optical films are provided on both sides, they may be the same or different. Further, in shape In the case of a liquid crystal display device, for example, one or two or more diffusion layers, an antiglare layer, an antireflection film, a protective plate, a tantalum array, a lens array sheet, a light diffusion sheet, a backlight, and the like may be disposed at appropriate positions. Components.

Example

Hereinafter, the invention will be specifically described by way of examples, but the invention is not limited by the examples. It should be noted that the parts and % in each example are based on the weight. Hereinafter, room temperature standing conditions which are not specifically defined are 23 ° C and 65% RH.

<Measurement of Weight Average Molecular Weight of (Meth)Acrylic Polymer>

The weight average molecular weight of the (meth)acrylic polymer is measured by GPC (gel permeation chromatography).

‧Analytical device: manufactured by Tosoh Corporation, HLC-8120GPC

‧Column column: made by Tosoh Corporation, G7000H _XL +GMH _XL +GMH _XL

‧Tube size: 7.8mmφ×30cm each, total 90cm

‧column temperature: 40 ° C

‧Flow: 0.8ml/min

‧Injection amount: 100μl

‧Extraction solution: tetrahydrofuran

‧Detector: Differential Refractometer (RI)

‧Standard sample: polystyrene

<Iodine content in polarizer>

Regarding the iodine content (the content of iodine and/or iodide ions) in the polarizer, the intensity of the fluorescent X-ray is measured for a polarizer containing a predetermined amount of potassium iodide, and the iodine content is derived. The relationship between the amount and the intensity of the fluorescent X-ray. The fluorescent X-rays of the iodine-based polarizer having an unknown iodine content were measured, and the amount of iodine was calculated from the numerical value using the above relational expression.

<Production of polarizing film (1)>

In order to produce a thin polarizer, first, a laminate having a PVA layer having a thickness of 9 μm formed on an amorphous PET substrate is subjected to air-assisted stretching at a stretching temperature of 130° C. to form a stretched laminate, which is then pulled. The stretched layer body was immersed in a dyeing liquid containing 0.1 part by weight of iodine and 0.7 part by weight of potassium iodide with respect to 100 parts by weight of water to form a colored layered body. Further, the colored laminate was stretched by boiling in water of boric acid having a stretching temperature of 65 degrees to have a total stretching ratio of 5.94 times, thereby producing an optical film comprising a 4 μm thick PVA layer integrally stretched with the amorphous PET substrate. Laminated body. Through the two-stage stretching as described above, an optical thin film laminate including a PVA layer having a thickness of 4 μm, which constitutes a high-functional polarizing layer which is formed into a film, is formed. The PVA molecules of the PVA layer on the PET substrate are highly oriented, and the dyed adsorbed iodine is highly oriented in one direction in the form of a polyiodide complex. Further, a polyvinyl alcohol-based adhesive is applied to the surface of the polarizing layer of the optical film laminate, and a saponified 40 μm-thick triethylene fluorene cellulose film is bonded thereto, and then the amorphous PET substrate is peeled off. A polarizing film using a thin iodine-based polarizer and having a transparent protective film on only one side is used. Hereinafter, this is called a polarizing film (1). The thin iodine-based polarizer has an iodine content of 5.1%.

<Production of polarizing film (2)>

A polyvinyl alcohol film having a thickness of 80 μm was stretched to 3 times while being dyed in a 0.3%-concentration iodine solution at 30 ° C for 1 minute between rolls having different speed ratios. Then, it was immersed in an aqueous solution containing 4% of boric acid and 10% of potassium iodide at 60 ° C for 0.5 minutes while stretching to a total stretching ratio of 6 times. Subsequently, it was immersed in an aqueous solution containing potassium iodide at a concentration of 1.5% at 30 ° C for 10 seconds for washing, and then dried at 50 ° C for 4 minutes to obtain an iodine-based polarizer having a thickness of 20 μm. A saponified triacetonitrile cellulose film having a thickness of 40 μm was attached to both surfaces of the polarizer by a polyvinyl alcohol-based adhesive, and a thickness of 33 μm was attached to the other surface of the polarizer. The olefin-based film is formed into a polarizing film having a transparent protective film on both sides of the iodine-based polarizer. Hereinafter, this will be referred to as a polarizing film (2). The iodine-based polarizer had an iodine content of 6.2%.

<Production of polarizing film (3)>

A polarizing film was produced by the same operation except that the immersion time in the dyeing liquid in the preparation of the polarizing film (1) was changed to 65 seconds. Hereinafter, this is called a polarizing film (3). The iodine-based polarizer had an iodine content of 5.9%.

<Production of polarizing film (4)>

A polarizing film was produced by the same operation except that the immersion time in the dyeing liquid in the production of the polarizing film (1) was changed to 60 seconds. Hereinafter, this is called a polarizing film (4). The iodine-based polarizer had an iodine content of 4.1%.

Manufacturing example 1 <Preparation of acrylic polymer (A-1)>

A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was placed in a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. Then, 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator and ethyl acetate were put into the flask together with 100 parts of the above-mentioned monomer mixture (solid content), and stirring was carried out while introducing nitrogen gas to carry out nitrogen. take Then, the temperature of the liquid in the flask was maintained at around 60 ° C, and polymerization was carried out for 7 hours. Then, ethyl acetate was added to the obtained reaction liquid to prepare a solution of the acrylic polymer (A-1) having a solid concentration of 30% and a weight average molecular weight of 1.6 million.

Manufacturing Example 2 <Preparation of acrylic polymer (A-2)>

In the production example 1, acrylic acid having a weight average molecular weight of 1.6 million was prepared in the same manner as in Production Example 1 except that a monomer mixture containing 99 parts of butyl acrylate and 1 part of acrylic acid was used. A solution of the polymer (A-2).

Manufacturing Example 3 <Preparation of iodine aqueous solution>

An aqueous solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.0% by weight was prepared.

Example 1 (Preparation of optical adhesive)

0.1 part by weight of trimethylolpropane decyl diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.: TAKENATE D110N) was added to 100 parts of the solid content of the acrylic polymer (A-1) solution obtained in Production Example 1. An acrylic adhesive solution was prepared by using 0.3 parts of benzophenone oxide and 0.075 parts of γ-glycidoxypropyl methoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) as a crosslinking agent.

(Production of polarizing film with adhesive layer)

Next, the above acrylic adhesive solution is applied as a spray coater. The surface of the polyethylene terephthalate film (spacer film) treated with the polyoxynene stripper was uniformly applied and dried in an air circulating oven at 155 ° C for 2 minutes in a spacer film. The surface formed an adhesive layer having a thickness of 20 μm. Next, on the side of the polarizer of the one-side protective polarizing film (1) produced as described above, the adhesive layer formed on the spacer film was transferred to form a polarizing film with an adhesive layer.

Examples 2 to 12 and Comparative Examples 1 to 2

In the first embodiment, when the optical adhesive was prepared, the components were blended as shown in Table 1, and when the polarizing film with the adhesive layer was formed, the type of the polarizing film was changed as shown in Table 1, and A polarizing film with an adhesive layer was produced in the same manner as in Example 1. In the examples 8 and 9, when the optical adhesive was prepared, 0.1 part of the aqueous iodine solution prepared in Production Example 3 was blended in addition to the crosslinking agent and the decane coupling agent.

The polarizing film with the adhesive layer obtained in the above Examples and Comparative Examples was subjected to the following evaluation. The evaluation results are shown in Table 1.

<Iodine Analysis: ESCA>

The iodine content (iodine and/or iodide content: atomic %) of the adhesive layer obtained in each example was measured by ESCA.

The measurement method of ESCA is as follows.

‧Installation; Ulvac-phi. Quantum 2000

‧X-ray source; monochromatic Al Kα

‧Xray Setting;200μmφ[30W(15kV)]

‧ photoelectron sweep angle; 45 degrees relative to the surface of the sample

‧ Neutralization conditions; neutralizing gun and Ar ion gun (neutralization mode)

‧Ar ion gun acceleration voltage (grating size); 1kV (2mm × 2mm)

‧Ar ion gun etching rate (SiO2 conversion value); about 2nm/min

Preparation of sample: For the sample (adhesive layer), a sample piece cut into a size of about 10 mm square was pressed against the sample stage with a Mo plate and fixed.

Evaluation method: The sample was subjected to depth direction analysis (measured by depth analysis by Ar ion etching), and the element ratio (atomic %) at each depth level was calculated.

<Iodine Analysis: TOF-SIMS5>

The iodine content (the content of iodine and/or iodide ions) of the adhesive layer obtained in each of the examples was measured by TOF-SIMS5 manufactured by ION-TOF. The measurement method is as follows.

Adjustment of the sample: The sample (adhesive layer) cut into 1 cm square was frozen, and subjected to precision tilt cutting, and then measured.

The measurement conditions are: irradiation of primary ions; Bi ₃ ²⁺

Primary ion acceleration voltage; 25kV

Measuring area: 300~350μm square

In addition, the amount of iodine in each case is based on the intensity ratio of the secondary ionic strength C ₃ H ₃ O ₂ ^- derived from butyl acrylate to the secondary ion intensity I ^- derived from iodine (I ^- /C ₃ H ₃ O ₂ ^- ) indicates the amount of iodine contained in the adhesive layer.

<surface resistance value: initial stage>

After the separator film of the polarizing film with the adhesive layer was peeled off, the surface resistance value (Ω/□) of the surface of the adhesive was measured using MCP-HT450 manufactured by Mitsubishi Chemical Corporation.

<Evaluation of static electricity unevenness>

The produced polarizing film with an adhesive layer was cut into a size of 100 mm × 100 mm, and attached to a liquid crystal panel. The panel was placed on a backlight having a luminance of 10,000 cd, and ESD (ESD-8012A, manufactured by SANKI Corporation) as an electrostatic generating device was used to generate static electricity of 5 kV, thereby causing disorder of alignment of the liquid crystal. The recovery time (seconds) of the display failure due to the above-described orientation failure was measured by an instantaneous multi-channel photodetector (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.), and the evaluation was performed based on the following criteria.

◎: The display failure disappeared in less than 1 second.

○: The display failure disappeared in less than 1 second and less than 10 seconds.

×: The display failure disappeared after 10 seconds or more.

<Durability (stripping and foaming)>

The spacer film of the polarizing film with the adhesive layer was peeled off, and adhered to an alkali-free glass (manufactured by Corning Incorporated, 1737) having a thickness of 0.7 mm using a laminator. Next, autoclaving was performed for 15 minutes at 50 ° C and 0.5 MPa, and the polarizing film of the above-mentioned adhesive layer was completely adhered to the alkali-free glass. Then, the mixture was placed in a heating oven (heating) at 80 ° C and 90 ° C, and evaluated for the peeling of the polarizing film after 500 hours under the following conditions on a 60 ° C / 90% RH constant temperature humidifier (humidification).

◎: No peeling or foaming was found at all.

○: Peeling or foaming which was not visually confirmed was found.

△: Small peeling or foaming which was confirmed by visual observation was found.

×: Significant peeling or foaming was found.

In Table 1, "C-1" in the ionic compound (C) represents 1-ethyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, and "C-2" represents Lithium bis(trifluoromethanesulfonyl) ruthenium iodide; "D-1" in the antioxidant (D) means Irganox 1010 manufactured by BASF Corporation; "E-1" in the crosslinking agent (E) means Mitsui Takeda Isocyanate cross-linking agent (TAKENATE D110N, trimethylolpropane decyl diisocyanate) manufactured by Chemical Co., Ltd., "E-2" means benzoyl peroxide (Niper BMT) manufactured by Nippon Oil & Fat Co., Ltd.; decane coupling agent (F "F-1" in the middle of the company is KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.

Claims (19)

An optical adhesive layer comprising an optical adhesive containing a base polymer (A) and containing iodine and/or iodide ions (B). The optical adhesive layer according to claim 1, which contains 0.02 to 1 atom% of the aforementioned iodine and/or iodide ion (B). The optical adhesive layer according to claim 1 or 2, wherein the base polymer (A) is a (meth)acrylic polymer containing an alkyl (meth)acrylate as a monomer unit. The optical adhesive layer according to claim 1 or 2, wherein the aforementioned base polymer (A) contains a hydroxyl group. The optical adhesive layer according to claim 1 or 2, wherein the base polymer (A) is a (meth)acrylic polymer containing an alkyl (meth)acrylate and a hydroxyl group-containing monomer as a monomer unit. The optical adhesive layer according to claim 1 or 2, wherein the aforementioned base polymer (A) contains a carboxyl group. The optical adhesive layer according to claim 1 or 2, wherein the base polymer (A) is a (meth)acrylic polymer containing an alkyl (meth)acrylate and a carboxyl group-containing monomer as a monomer unit. The optical adhesive layer according to claim 3, wherein the (meth)acrylic polymer contains butyl (meth)acrylate as the alkyl (meth)acrylate serving as a monomer unit, and the optical adhesive is used. The agent layer contains the aforementioned iodine and/or iodide ion (B) at a value of 0.01 to 3 of I ^- /C ₃ H ₃ O ₂ ^- . The optical adhesive layer of claim 1 or 2, which further contains an ionic compound (C). The optical adhesive layer according to claim 9, wherein the ionic compound (C) is an alkali metal salt and/or an organic cation-anion salt. The optical adhesive layer of claim 1 or 2, which further contains an antioxidant (D). The optical adhesive layer of claim 1 or 2 further comprising a crosslinking agent (E). The optical adhesive layer of claim 1 or 2 further comprising a decane coupling agent (F). An optical film with an adhesive layer, comprising: an optical film; and an optical adhesive layer according to any one of claims 1 to 13 provided on at least one side of the optical film. The optical film of the adhesive layer of claim 14, wherein the optical film is a polarizing film. The optical film of the adhesive layer according to claim 15, wherein the polarizing film is an iodine-based polarizing film having a transparent protective film on at least one side of the iodine-based polarizing member containing iodine and/or iodide ion (B). The optical film of the adhesive layer of claim 16, wherein the iodine-based polarizer contains 3 to 10% by weight of iodine and/or iodide ion (B). The optical film with an adhesive layer according to any one of claims 15 to 17, wherein the polarizing film has a transparent protective film only on one side of the polarizing member, and the optical adhesive layer is disposed on the polarizing member without the foregoing One side of the transparent protective film. An image display device characterized in that at least one is used The polarizing film of the adhesive layer of any one of items 14 to 18.